DE3340114A1 - METHOD FOR PRODUCING 2-AMINO-1-HYDROXY-4- OR -5- (SS-SULFATOAETHYLSULFONYL) BENZOLE COMPOUNDS AND THE USE THEREOF FOR SYNTHESIS OF FIBER-REACTIVE COMPOUNDS - Google Patents

Description

2 ύ J ^L. J i ι

HOECHST AKTIENGESELLSCHAFT HOE 83 / F 231 Dr.ST/sch

Process for the preparation of 2 ~ amino-1-hydroxy-4- or -5 - (# - sulfatoäthylsulfonyl) benzene compounds and their use for the synthesis of fiber- reactive compounds

The invention is in the technical field of esterification of intermediates that are particularly suitable for dye synthesis.

It is known, o-Arainophenol connections that have a j2> -Hydroxyäthylsulfonyl ~ group by SuIfatierungsmittel in their Schwefelsäurehalbester connections (ß-sulfatoethylsulfonyl-aminophenol nnectivity) convert. These / ä-Sulfatoäthylsulfonyl-aminopbenole are used

Ί0 as starting compounds for the production of fiber-reactive, fiber-finishing compounds (cf. also ÜS-PS 2 670 265), such as fiber-reactive dyes, the one or more of these ß-sulfatoethylsulfonyl groups contain. In particular, these ε-sulfatoethylsulfonyl-aminophenols can be used in per se known procedures, which are described in large numbers in the literature, fiber-reactive azo dyes and their Synthesize metal complex compounds or metal complex formazan dyes.

The known processes for the preparation of these sulfuric acid half esters however, show certain shortcomings or disadvantages which seem necessary for further improvement let.

For example, from the German patent specifications 938 145 and 953 103, from US Patents 3,135,730 and 3,364,194 and from British Patents

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Publications 83I 128 and 1 075 074 known, ß-Hydroxyäthylsulfonylaminophenole with 6 times the molar amount of. concentrated (ie 90-95% strength by weight) sulfuric acid, thus with a 500% excess of esterifying agent, to esterify into the corresponding β-sulfatoethylsulfonyl-aminophenols. When using this excess of esterifying agent, the reaction medium is indeed a solution, so that the esterification reaction can be carried out relatively easily in conventional stirred vessels, such as are generally used and available in chemical laboratories and factories; unsatisfactory and disadvantageous here, however, is the work-up of the relatively high excess of esterifying agent, for example by precipitation as calcium sulfate (gypsum), which must be dumped if the esterifying agent is not to get into the wastewater in the form of soluble salts (sodium sulfate). Furthermore, with this method of esterification in a 500% excess of concentrated sulfuric acid, no fully satisfactory sulfation of the β-hydroxyethylsulfonyl group is achieved. Quantitative investigations with the aid of thin layer chromatography (TLC) and high pressure liquid chromatography (HPLC) show that the starting β-hydroxyethylsulfonylaminophenols remain unesterified to an extent of 10% or more. The degree of esterification of this procedure is therefore at most 90 % of theory, so that the further processing of ß-sulfatoethylsulfonyl-aminophenols, known per se, to give corresponding fiber-reactive compounds, such as dyes, leads to end products, • the 10 % and more of non-fiber-reactive end product ( hereinafter referred to as dye for the sake of simplicity). This inactive part of the dye cannot react with the fiber, so that it is not fixed on the fiber and ends up in the wastewater.

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Furthermore, from Example 2 of US Pat. No. 3,414,579, 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyD-benzene) is known with 3> 6 times the molar amount of sulfamic acid in pyridine as solvent in the corresponding Transfer sulfato compound. Although this means in comparison to the previously described method a significant reduction in the excess of esterifying agent, but the pyridine must be removed from the Reaction batch can be removed, for example by distillation under reduced pressure. One complete Removal of the pyridine is not possible, however, and it gets into the further processing of the manufactured Sulfuric acid half ester compound into a fiber-reactive end product (dye) in the mother liquor of the reaction mixture. However, it is absolutely necessary to remove the pyridine from this before the wastewater in may enter the sewerage system.

A further reduction in the excess of esterifying agent in the sulfation of β-hydroxyethylsulfonyl-aminophenols is possible according to the procedure of US Pat. No. 4,334,076; here an excess of esterifying agent of up to 120% is used. Working with such a small excess is only possible with the help of machines that work with a kneading effect. The use of kneaders does not only mean a technically very complex way of working, but also represents a special and. This is an expensive investment for a company, since such kneaders are generally not available in the laboratory or factory compared to the agitated vessels commonly used in chemical engineering. The applicability of this process is therefore dependent on kneaders that are generally not available in chemical plants and is therefore limited.

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However, disadvantages are evident in the use at sulfating agents in an excess not only in the work-up of the excess esterifying agent, but also, under certain circumstances in the reaction itself, the sulfation provided by lOOXiger sulfuric acid or sulfur trioxide-containing sulfuric acid at temperatures above 12O ⁰ C "is performed. In In this case, not only esterification (sulfation) of the β-hydroxyethylsulfonyl group takes place, but “also sulfation of the benzene nucleus, ie, additional introduction of a sulfo group (see British Patent Specification 1,372,368, page 2, line 41 et seq., and Example 1).

In addition, attempts have been made to sulfate ß-Hydroxyäthylsulfonylaminophenolen using only small excesses of esterifying agent (chlorosulfonic acid or sulfur trioxide) by working in Improve N-methyl-pyrrolidone as a solvent. However This process also has the major disadvantage that a subsequent extraction of the solvent with the help of of chlorinated hydrocarbons, such as methylene chloride or chloroform, is required, which is a significant Expenditure on safety precautions required.

There was thus a technical interest and the task of developing a process for the sulfation of ß-hydroxyethylsulfonyl-aminophenols to find that without the addition of an organic solvent and also without the need the use of kneaders (which are required for batches that cannot be stirrable) in the usual and

* common, commonly used in chemical laboratories and factories available stirred vessels (stirred kettles) with the smallest possible amounts of esterifying agents and nevertheless with a high degree of esterification can be carried out without an additional suIfierungsreaktion.

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Preliminary work on this has shown that if you use concentrated sulfuric acid according to the prior art works as an esterifying agent and at the same time as a solvent, a reduction in the esterifying agent below the 6-fold molar amount leads to a lowering of the degree of esterification.

With the present invention, there has now been a method
found with. the ß-Hydroxyäthylsulfonyl-aminophenole

surprisingly with an extremely high degree of esterification (97 % and higher) and without noticeable sulphonation
can be converted into their sulfuric acid half-ester compounds using small excesses of sulfating agents.

The present invention thus relates to a method
for the preparation of ß-sulfatoethylsulfonyl-aminophenol compounds of the general formula (1) by reacting ß-hydroxyethylsulfonyl-aminophenol compounds of the general formula (2)

OH

R X

(2)

in which one Y is the ß-sulfatoethylsulfonyl group of the formula -SO ₂ -CH ₂ -CH ₂ -OSOoH and the other
Y represents a hydrogen atom which one X represents
ß-Hydroxyäthylsulfonyl group of the formula

-SO ₂ -CH ₂ -CH ₂ -OH and the other X is a hydrogen atom and R is a hydrogen atom or a
An alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, a chlorine atom, a bromine atom or

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the nitro group is, with a sulfuric acid / sulfur trioxide mixture as the sulfating agent, which is characterized in that the sulfation is carried out using a sulfation mixture which consists of 1.5 to 4 times the molar amount of 100% sulfuric acid and the 0.9-fold to 1.1-fold molareruMenge of sulfur trioxide, based on mole of the starting compound (2), and in that to effect the reaction in usual stirred vessels, the no kneading, at a temperature between 0 ⁰ C and 12O ⁰ C , preferably between 40 and 100 ^° C., keeping the temperature so high within this temperature range that the reaction mixture remains sufficiently fluid and thus stirrable.

Due to the consumption of sulphating agent and thus also of solvent in the sulphating reaction of the The method according to the invention changes the consistency of the reaction medium with an increase in viscosity and optionally with precipitation of solids, such as End product (1) that are no longer dissolved in the reaction medium. This can be counteracted by increasing the reaction temperature, whereby it is useful to keep the reaction temperature only as high as is necessary for the stirrability of the reaction medium. This can, if necessary in preliminary tests, depending on the choice of the starting aminophenol compound and the Easily determine the amount of esterifying agent and - even in large technical approaches - easily control it.

As a rule, a higher reaction temperature is required if a lower amount of sulfuric acid is used in the according to the invention specified range between 1.5 to 4 moles per mole of starting aminophenol are used. .

A sulfation mixture is preferably used

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Sulfuric acid and sulfur trioxide, the proportion of 2 to 3 times the molar amount of 100% sulfuric acid and / or the 0.95 times to 1.1 times the molar amount of sulfur trioxide, based in each case on the mole of starting aminophenol (2) contains. As a rule, the proportion of 10% sulfuric acid is within the specified range according to the invention Increase limits if a lower amount of sulfur trioxide, such as the lower one Amount of 0.9 moles of sulfur trioxide per mole of aminophenol (2), is used as a sulfating agent mixture to produce a to ensure a sufficiently high degree of esterification.

It is essentially irrelevant in what way the reaction components (starting aminophenol of the formula (2), sulfuric acid and sulfur trioxide or oleum) are combined with one another. So you can do the sulfation mixture the composition previously defined according to the invention from hydrous sulfuric acid, for example with a water content of up to 10 wt .- *, which is usually technically accessible, and sulfur trioxide and combine this sulfation mixture with the aminophenol compound (2). One can however, also the aminophenol compound (2) beforehand in water-containing sulfuric acid or 100% sulfuric acid and the appropriate amount of sulfur trioxide or higher concentrated oleum for the appropriate setting add the sulfation mixture composition or the aminophenol (2) with oleum as appropriate Combine the composition to then carry out the actual sulfation reaction. You give that Aminophenol (2) initially only with 100% sulfuric acid or with hydrous sulfuric acid, for example more than 90% by weight combined, is already done in a considerable amount Extent the sulfation reaction; to achieve the desired very high degree of esterification however, the addition of that specified according to the invention

Sulfur trioxide content is absolutely necessary.

The method according to the invention can, for example, in a technically advantageous embodiment can be carried out in such a way that one in the stirred vessel (stirred tank) a mixture of sulfuric acid and sulfur trioxide. of the specified composition and the starting compound (2) enters and here the reaction mixture by means of the released heat of reaction, against if necessary by additional external heat input, yourself heats up within the specified temperature range or increases its temperature, and only to the extent that as the consistency of the reaction mixture remains sufficiently thin to use in normal stirred vessels sufficient stirring and mixing can take place.

ß-Hydroxyäthylsulfonyl-aminophenol -verbindungen der General formula (2), which serve as starting compounds in the process according to the invention, are for example 2-amino-1-hydroxy-4- (S-hydroxyethylsulfonyl) benzene, 2-amino-l-hydroxy-5- (ß-hydroxyethylsulfonyl) benzene, 2-amino-l-hydroxy-4-methyl-5- (ß-hydroxyäthy! Sulfonyl) -benzene, 2-Amino-1-hydroxy-4-methoxy-5- (ß-hydroxyäthy1-sulfonyD-benzene, 6-chloro-2-amino-l-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene, 6-bromo-2-amino-l-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene, 2-Amino-1-hydroxy-5-methoxy-4- (ß-hydroxyäthyIsulfonyl) -benzene and 6-nitro-2-amino-1-hydroxy-4- (ß-hydroxyethy1sulfonyl) benzene.

The work-up of the reaction mixture after the esterification can in and of itself be customary and can be carried out by the person skilled in the art in a familiar and familiar manner. For example, the reaction mixture with ice and water diluted at low temperature and using a

- & ■ - ■

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common basic alkali metal compound, such as sodium bicarbonate or sodium carbonate or the corresponding potassium compound, neutralized. The neutral or very weakly acidic solution is then evaporated to dryness or spray dried. This gives the alkali metal salts of the compounds of the general Formula (1) mixed with the alkali metal sulfate, such as sodium sulfate. Another possibility of working up the reaction mixture after the esterification is that one it is neutralized with calcium carbonate after dilution with ice / water, the precipitated calcium sulfate is sucked off, to the filtrate oxalic acid and a basic alkali metal salt such as alkali bicarbonate or carbonate is added to it to free calcium ions in the weakly acidic range, separating the calcium oxalate precipitate, for example by filtration or centrifugation, and the filtrate is then evaporated to dryness or spray-dried. In this way the alkali metal salts are obtained Compounds (2) free from alkali metal sulfates,

The ß-sulfatoethylsulfonyl-aminophenol compounds thus obtained of the general formula (1) can then advantageously be used as starting materials for the production of strong dye products that have practically no fiber-inactive dye content, are further processed.

It is advantageous, however, instead of that according to the invention prepared compounds of the general formula (1) first to isolate them directly in their reaction mixture of the synthesis of fiber-reactive end products (Dyes) to be supplied. Since the compounds of the general formula (1) are used, for example, as diazo components for the production of azo dyes and their metal complex compounds can serve, the

Synthesis approach after completion of the esterification reaction directly - after prior dilution with ice / water without use additional acid in the diazotization reaction. This is how the esterification mixture diluted with ice / water is used at the same time as a reaction medium for the diazo-'tierungsreaktion carried out in and of itself customary with an alkali metal nitrite as well as for the subsequent coupling reaction with a Coupling component after (partial) neutralization of the acid to a pH range in which the coupling usually occurs is carried out. In the same reaction medium can be used to synthesize the metal complex compounds in a procedure that is customary in and of itself and has been described many times in the literature can be carried out, the metal-donating compounds customary for this purpose are added. This direct use of the esterification approach as a "diazo component" is not only advantageous in the production of metal complex formazan compounds, such as in particular copper complex formazan compounds (Dyes), but also particularly advantageous in the production of 1: 1 copper, 1: 2 cobalt and 1: 2 chromium complex azo compounds (metal complex dyes) or their metal-free azo compounds.

The direct use of the esterification approach not only has the advantage of working steps in isolation the sulfato compound of the general formula (1). and the chemicals required for this (acid-binding Saving funds), but also has the great advantage, especially in the production of the dyes, that the dyes themselves easily by evaporation or spray drying of the neutral or weakly acidic dye solution can be isolated without wastewater, since the electrolyte content is very low, so that a precipitation (Salting out) of the dyes using sodium chloride or

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Potassium chloride, which leads to salty sewage, is not required.

Since the dye solutions obtainable from the direct use of the esterification mixture are relatively are low in salt, the dye products produced in these solutions also have a sufficiently good one 'Solubility. The dye solutions prepared by the method described above can therefore, if necessary after concentration by partial evaporation, as concentrated, standardized dye solutions in be placed on the market as such directly, without the powdery dye itself from the user (Dyer) must first be weighed and dissolved in water, used for the preparation of the dye baths and dye liquors can be.

The from the sulfato compounds prepared according to the invention The dyes obtainable by the general formula (1) represent because of their very high degree of esterification Dye products which have only an extremely low proportion of fiber-inactive product (dye).

The following examples serve to explain the subject matter of the invention. Parts represent parts by weight and percentages relate to percentages by weight, unless otherwise stated. Parts by weight behave . to parts by volume like kilograms to liters.

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example 1

In a stirred vessel equipped with a stirrer (in technology, for example, a stirred tank; in the laboratory, a three-necked flask
be used with KPG stirrers) are mixed into a mixture
from 61 parts of 100% sulfuric acid (monohydrate) and

49.3 parts of 65% oleum within 10 to 15 minutes
87 parts of 2-amino-1-hydroxy-4- (ß-hylroxyäthylsulfonyl) benzene entered with stirring, the temperature
in the reaction mixture from initially 20 ⁰ C in the course of the
The entry gradually increases so that it is about 85 ^° C. after the entry is complete. After three hours of stirring at 80 to 85 ⁰ C, the esterification is completed.

A quantitative analysis of the reaction mixture can be carried out
carry out by thin layer chromatography (TLC) or by high pressure liquid chromatography (HPLC):
The esterification mixture contains 116-118 parts of 2-amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) benzene; the degree of esterification is at least 97% of theory; the proportion of unreacted 2-amino-1-hydroxy-4- (ß-hydroxyäthylsulfonyl) -benzene and likewise the proportion of sulfated product is in each case a maximum of 1%, based on the amount of
this starting compound

Example 1a

The esterification mixture obtained according to Example 1 with the
SuIfato compound prepared according to the invention, which is dissolved in the sulfuric acid, can be worked up as follows:

_ (aj_ The 80 to 85 ⁰ C hot esterification mixture is with
800 parts of ice and water combined, with on it
care is taken that the temperature of the resulting mixture does not exceed ^{10 0 C;} expediently one leaves the
hot reaction mixture on the vigorously stirred mixture

flow from ice and water. Those adhering to the vessel wall The remainder of the esterification mixture is rinsed out with ice and water.

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(b) The cold, dilute solution of the reaction product obtained under (a) is adjusted to a pH value between 5 and 6.5 by sprinkling in sodium bicarbonate ^{at a temperature of 20 ° C. or below while stirring.} The resulting solution, if necessary after prior clarification, for example by means of kieselguhr and filtration, is evaporated to dryness in the customary manner, for example in a circulating air cabinet or vacuum cabinet at 50 to 60 ° C. or advantageously by spray drying.

245 parts of a dry product are obtained which, on grinding, give a gray powder and which is the main component contains, in addition to sodium sulfate, 126 parts of the sodium salt of the sulfato compound mentioned.

(c) The cold, dilute solution of the synthesis product obtained under (a) is diluted with 200 parts of an ice / water mixture and adjusted to a pH between 5 and 6 with calcium carbonate ^{at a temperature of 25 ° C. or below.} The precipitate of calcium sulfate is filtered off at room temperature and washed with 1000 parts of water of 70 ⁰ C. 27 parts of oxalic acid dihydrate are added to the filtrate combined with the washing water and the pH is adjusted to between 5 and 6.5 using sodium bicarbonate. A further 20 parts of kieselguhr are added, the mixture is stirred for a further hour, filtered and the residue is washed with 200 parts of water. This filtrate, combined with the washing water, is evaporated to dryness as under (b).

130 parts of a dry product are obtained which, after grinding, give a gray powder and the sodium salt of 2-Amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) benzene almost free from salt contamination.

The cold, dilute solution obtained according to (a) or the Sulfuric acid esters obtained according to (b) or (c) or their sodium salts can advantageously be known per se

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Way of producing fiber-reactive compounds, in particular of fiber-reactive azo dyes or their Metal complex compounds or of fiber-reactive copper formazan dyes be used. 5

Example 1b

For working up the sulfuric acid ester prepared according to the invention of Example 1, the procedure is as in section (b) of Example 1a, but sodium bicarbonate is used by an equivalent amount of potassium bicarbonate or potassium carbonate. A dry product is obtained which as the main component in addition to potassium sulfate, the potassium salt of contains said sulfato compound.

Example 2

In a reaction vessel equipped with a stirrer, 87 parts of 2-amino-1-hydroxy-4- are added to a mixture of 139 parts of 100% sulfuric acid (monohydrate) and 49.3 parts of 65% oleum within 10 to 15 minutes with stirring. (ß-hydroxyethylsulfonyl) benzene was added while allowing the temperature in the reaction mixture from an initial 0 ⁰ C in the course of entering gradually increased so that it is 50 ⁰ C last. The mixture is subsequently stirred at 50 ^° C. for 4 hours; the esterification is then ended.

The quantitative analysis of the reaction mixture by means of TLC or HPLC shows the following:

The content of unreacted 2-amino-1-hydroxy-4- (ßhydroxyäthylsulfonyl) -benzene is below 1%, and the proportion of sulfated ester is less than 1 mol%. . The esterification mixture contains 116-118 parts of 2-amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) benzene corresponding to a degree of esterification of more than 97% of theory ...

The reaction mixture can be worked up according to Examples 1.

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Example 3

In a reaction vessel equipped with a stirrer, 87 parts of 2-amino-1-hydroxy-4- (ß -hydroxyäthylsulfonyl) -benzene entered, allowing the temperature in the reaction mixture ^{to rise gradually from initially 20 0} C in the course of the entry so that it is about 70 ⁰ C after the end of the entry. It is stirred for a further 4 hours at 60 to 70 ⁰ C; the esterification is then ended.

Analysis by TLC or HPLC shows that the esterification mixture 116-118 parts of 2-amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) benzene contains. The proportion of unchanged 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene is below 1%, based on the amount of this starting product used; the proportion of sulfated product is likewise with less than 1%. The degree of esterification is greater than 97% of the theory.

The mixture obtained with the esterification product can be worked up as described in Examples 1.

Example 4

In a reaction vessel with a stirrer, 87 parts of 2-amino-1-hydroxy-4- (ß -hydroxyäthylsulfonyl) ■ benzene entered, allowing the temperature in the reaction mixture ^{to rise gradually from initially 20 0} C in the course of the entry so that it is about 90 ⁰ C after the end of the entry. It is stirred at 90 to 100 ⁰ C for a further 3 hours; the esterification is then ended.

The analysis shows a degree of esterification of over 97% of theory. with 116-118 parts of 2-amino-i-hydroxy-4- (ß-sulfatoethyl-

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sulfonyl) benzene in an esterification mixture. The proportion of unchanged 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene is below 1.5%, the proportion of sulfated product is also below 1.5%, based on the used amount of this starting product.

Example 5

• In a reaction vessel with a stirrer, 139 parts of 100% sulfuric acid (which can be prepared by mixing 32.7 parts of 65% oleum with 106.3 parts of a (commercially available) 95.5% sulfuric acid) are 87 parts 2- amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene was added, maintaining the temperature at 50 - 60 ⁰ C allowed to rise. Is then added while continuing to stir at a temperature 50 to 70 ⁰ C still 49.3 parts of 65% oleum slowly added and stirred for 4 hours at 50 ⁰ C on. The esterification is then ended.

The analysis shows an esterification mixture with a content of 116-118 parts of 2-amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) benzene corresponding to a degree of esterification of greater than 97% of theory and a share of unchanged 2-Amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene and of sulfated product of less than 1% in each case, based on the amount of this starting product used.

. The esterification mixture can be worked up as described in Examples 1 and isolated as alkali metal salts will.

Example 6

In a reaction vessel equipped with a stirrer, 61 parts of 100% sulfuric acid are added while stirring from 30 minutes 87 parts of 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene entered, with one in the course

of the entry at the same time 49.3 parts of 65% strength oleum long. Sam adds and the temperature gradually increases to 80 ^° C

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leaves. The mixture is then stirred at 80-90 ^° C. for a further 3 hours.

The analysis shows that the esterification mixture is 116-118 Parts of 2-amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) benzene corresponding to a degree of esterification of greater than 97% of theory and unchanged 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene and sulfated product of less than 1% each, based on the amount of dor Contains starting compound.

Example 7

For the preparation of the isomeric compound according to the invention 2-Amino-1-hydroxy-5- (ß-sulfatoethylsulfonyl) benzene can one of the procedures given in Examples 1 to 6 above is used instead the 2-amino-1-hydroxy-4- (ß-hydroxyäthy! sulfonyl) -benzene the same amount of 2-amino-1-hydroxy-5- (ß-hydroxyäthy1-sulfonyl) -benzene a. The esterification proceeds in an identical manner with the same high degree of esterification and with the small proportions of by-products, as indicated in these Examples 1 to 6 for the isomeric compound. The esterification mixture with the 2-amino-1-hydroxy-5- (ß ~ sulfatoäthylsulfony]) - benzene can according to the procedures of Examples 1a and 1b worked up and converted into the alkali metal salts be transferred and isolated.

Examples 8-13

In the following table examples 8 to 13 are further ß-sulfatoethylsulfonyl-aminophenol compounds named according to the general formula (1) (here the formula radical M denotes hydrogen, sodium or potassium), which according to the invention from the corresponding ß-hydroxyethylsulfonyl-aminophenol compounds of the general formula (2) can be prepared. If you put one of these starting compounds of Examples 8 to for example in accordance with the details of the above examples

- VS -.

1 to 6 with a sulfuric acid / sulfur trioxide mixture, the corresponding sulfato compound is also obtained with a degree of esterification of greater than 9 7% of theory. and with the same high purity as stated there. These esterification mixtures can also be worked up and isolated analogously to the information in Examples 1a and 1b. You can in a known procedure for the production of fiber-reactive dyes, such as or azo dyes their metal complex compounds serve, where the sulfato compounds prepared with these according to the invention available end products (dyes) are characterized by a very low content of non-fiber-reactive dye and by corresponding advantageous properties, such as For example, high color yield when dyeing and printing cellulose fiber materials for fiber-reactive dyes known and customary dyeing processes.

E.g.

Output compound (2)

End product (1)

CH-

H,

HO-CH ₂ -CH ₂ -SO ₂

NH,

MO ₃ SO-CH ₂ -CH ₂ -SO ₂

0CH_ Cl OH ³

MO ₃ SO-CH ₂ -CH ₂ -SO ₂

NH,

MO ^ SO-CH ₀ -CH ₀ -SO,

NH,

E.g. Output compound (2) End product (1) OH NH ₂ OH CH30 / J- 12th CH ₃ O - ^ / - ^ ^TH 2 MO ₃ SO-CH ₂ -CH ₂ -SO ₂ HO-CH ₂ -CH ₂ -SO ₂ O ₂ N OH NH _? O ₂ N OH 13th MO ₃ SO-CH ₂ -CH ₂ -SO ₂ HO-CH ₂ -CH ₂ -SO ₂

Comparative example 1

Carrying out the sulfation according to Example 1 of German Patent 953 103:

In a reaction vessel equipped with a stirrer, 110 parts of 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene were dissolved in 325 parts of 90% aqueous sulfuric acid at a temperature of 30 - 35 ⁰ C was added. The reaction mixture was stirred for a further 6 hours until it was completely dissolved.

Analysis by TLC and HPLC showed a degree of esterification of 80% of theory. and a content of unchanged (unreacted) 2-Amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene from 20% of the starting compound used. If the reaction mixture is stirred for a further 24 hours, an unchanged, identical result is obtained.

Comparative example 2

Sulphation according to example 6 of German patent specification 1 126 542:

In a reaction vessel equipped with a stirrer 109 parts of 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene was added in 335 parts of concentrated (95.5% strength) sulfuric acid at 30 ⁰ C. The batch was stirred further at this temperature.

SAD

Both after 6 and after 24 hours, analysis by TLC and HPLC showed a degree of esterification of 90% of theory. with a residual content of 10% of the starting compound used.

Comparative example 3

Sulphation according to example 1b of German patent specification 1 233 9 63:

In a reaction vessel equipped with a stirrer, 109 parts of 2-amino-1-hydroxy-4- (ß-hydroxyethylsulfonyl) benzene were added to 180 parts by volume (corresponding to 332 parts) of concentrated (9 5.5%) sulfuric acid at a temperature of 70 - 80 ⁰ C entered. It was then 3 0 minutes at 70 - stirred 80 ⁰ C; thereafter the product was completely dissolved.

Analysis by TLC and HPLC showed that the reaction mixture still contained 10% of the 2-amino-1-hydroxy-4- (β-hydroxyethylsulfonyl) benzene used contained.

Comparative Example 4

It was made according to the procedure of the comparative example

proceed, but instead of the 335 parts of concentrated sulfuric acid specified there, only 257 parts of concentrated Sulfuric acid used. After a reaction time of 6 hours and also after a reaction time of For 24 hours the analysis still showed a content of the ß-hydroxyethylsulfonyl starting compound used of 13%.

Comparative example 5

It was made according to the procedure of the comparative example 2, but instead of the 335 parts of concentrated sulfuric acid specified there, only 205 parts were used concentrated sulfuric acid used. After a reaction time of 6 and also of 24 hours, the showed Analysis that the reaction mixture still contains 15% of the

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put ß-Hydroxyäthylsulfonyl starting compound contained.

Application example 1

A cold, dilute solution of the esterification product with 118 parts of 2-amino-1-hydroxy - ^ - (ß-sulfatoethylsulfonyl) benzene, prepared according to Example 1a, section (a), is added by adding an aqueous solution of 28 parts of sodium nitrite with stirring 0 to 10 ⁰ C diazotized. A small excess of nitrite is then destroyed with a little sulfamic acid. To produce an azo compound, 102 parts of 1- (4'-sulfophenyl) -3-methyl-pyrazolone (5) are added, the pH is adjusted to 5.5 to 6.5 with sodium carbonate and the coupling reaction is carried out while maintaining this pH range brought to the end. 100 parts of copper sulfate pentahydrate are then added, and the pH is adjusted to 5 to 5.5 with 20 parts of crystallized sodium acetate and further with sodium carbonate. The mixture is stirred for a further 3 hours at room temperature, the synthesis is clarified with the addition of kieselguhr and by filtration and the copper complex azo dye prepared of the formula is isolated

SO ₃ Na

CH ₀ -CH ₀ -OSO ₀ Na

- by evaporating the dye solution at 50 to 60 ⁰ C in a circulating air cabinet or in a vacuum oven or by spray drying. The residue is ground; it results in a yellow-brown dye powder, which is used when dyeing or printing cotton or other cellulose fiber material according to the usual printing methods for fiber-reactive dyes.

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and dyeing methods provides strong, yellow dyeings and prints with very good light and wet fastness properties. The received Dye powder is particularly notable for the fact that it only contains a small proportion of non-fiber-reactive substances Contains dye.

Application example 2

A cold, dilute reaction solution with 118 parts of 2-amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) -benzene prepared according to Example 1a, section (a) is prepared by adding an aqueous solution of 28 parts of sodium nitrite with stirring at 0 to 10 ⁰ C diazotized. A small excess of nitrite is then destroyed with sulfamic acid. The neutral aqueous solution of a monoazo dye composed of 2-aminonaphthalene-4,8-disulfonic acid as the diazo component and 1,3-dihydroxybenzene as the coupling component is added to this solution of the diazonium salt (the solution of the monoazo dye can be prepared as follows: 121 parts of 2-aminonaphthalene- 4,8-disulfonic acid is diazotized with an aqueous solution of 28 parts of sodium nitrite in 1000 parts of ice and water with the addition of 80 parts of a 30% strength aqueous hydrochloric acid at 0 ° to 10 ° C. A slight excess of nitrite is then destroyed as usual with aminosulfonic acid. 44 parts of 1,3-dihydroxybenzene are then added and stirring is continued until the coupling is complete, the batch is then adjusted to a pH between 6 and 7 using 33% strength aqueous sodium hydroxide solution).

The coupling reaction of the monoazo compound with the diazonium salt of the sulfato compound prepared according to the invention takes place at room temperature and a pH value of 6 to 6.5, which is set by sprinkling in calcium carbonate will. The reaction mixture is stirred until the coupling reaction has ended. Then you give Preparation of a copper complex disazo dye 100 parts Adding copper sulfate pentahydrate, adjusts the pH value by means of

33401 H.

Calcium carbonate to 5 to 5.5, the reaction mixture is heated to 40-5O ⁰ C, stirred for a further hour at this temperature and then filtered off the calcium sulfate formed, which is washed out ^{with water at 70 0 C.} The combined washing water and filtrate are mixed with 30 parts of oxalic acid dihydrate, then adjusted to a pH value between 5 and 5.5 with sodium carbonate, • after adding 20 parts of kieselguhr, stirred for 2 hours and then filtered.

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The 1: 1 copper complex disazo dye thus prepared is either by salting out with sodium chloride and / or potassium chloride and filtration or by spray drying isolated. However, due to the low content of inorganic salts, the dye solution can also be used without isolation the dye directly, if necessary after concentrating by evaporating the solution to a smaller volume, for dyeing or printing cellulose fiber material according to printing and dyeing processes customary for fiber-reactive dyes can be used. This 1: 1 copper complex disazof arbstof f, from the 2-amino-1-hydroxy-4- (ß-sulfatoethylsulfonyl) benzene prepared according to the invention as Starting compound was synthesized, provides both after isolation as a dry powder and under Application in concentrated solution on cellulose fiber materials according to the usual for fiber-reactive dyes . Printing and dyeing process due to its low proportion of non-fiber-reactive dye reddish brown dyeings and prints with very good light and wet fastness properties, which are stronger in color than those dyeings and prints which was prepared with the product of such a dye for which a starting sulfato compound was used, the was esterified by a prior art method.

Claims (5)

Patent claims: 1./Process for the production of ß-sulfatoethylsulfonyl-L. · "Aminophenol compounds of the general formula (1) by reaction of ß-Hydroxyäthylsulfonylaminophenol compounds of the general formula (2) OH OH NH _{2 R} fVH ₂ Y I X Y X in which one Y is the ß-sulfatoethylsulfonyl group of the formula -SO ₂ -CH ₂ -CH ₂ -OSOoH and the other Y is a hydrogen atom, the one X is a ß-hydroxyethylsulfonyl group of the formula -SO ₂ -CH ₂ - CH ₂ -OH and the other X is a hydrogen atom and R is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, a chlorine atom, a bromine atom or the nitro group, with a sulfuric acid / Sulfur trioxide mixture as sulphating agent, characterized in that the sulphation is carried out using a sulphation mixture which is proportionally composed of 1.5 times to 4 times the molar amount of 100% sulfuric acid and 0.9 times to 1, 1-fold molar amount of sulfur trioxide, based on mole of the starting compound (2), and in that one carries out the reaction in the usual stirred vessels, at a temperature between O ⁰ C and 12O ⁰ C and in this case within this temperature range, the temperature as high h Old that the reaction mixture remains sufficiently fluid and stirrable. t «- - SAD ORIGINAL _o ". ^ _{Λ Λ} . - £ 5 - HOE 83 / F 231 3 O '-. -JII 4 2. The method according to claim 1, characterized in that a sulfation mixture is used, whose proportional amount of 100% sulfuric acid is 2 to 3 times the molar amount, based on the starting compound (2), is. 3. The method according to claim 1 or 2, characterized in that the proportional amount of sulfur trioxide the 0.95 times to 1.1 times the molar amount, based on starting compound (2). 4. The method according to claim 1, 2 or 3, characterized in that the reaction is carried out at a temperature between 40 and 10O ⁰ C. 5. Use of the compounds of general prepared by a process according to claim 1, 2, 3 or 4 Formula (1), preferably in the form of the esterification batch, for the synthesis of fiber-reactive compounds, preferably dyes. BATH ORIGINAL